Process for the preparation of stable dispersions of polyisocyanate-polyaddition products in hydroxyl containing compounds

ABSTRACT

This invention relates to a process for the in situ preparation of stable dispersions of polyisocyanate-polyaddition products in hydroxyl containing compounds as dispersing agent by a process which comprises reacting 
     (1) organic polyisocyanates with 
     (2) compounds having primary and/or secondary amino groups and/or primary hydroxyl groups and/or ammonia, in 
     (3) compounds having at least one hydroxyl group, wherein 
     compounds (3) have secondary hydroxyl groups in cases when compounds (2) have primary hydroxyl groups and wherein the components are reacted in the presence of more than 4% by weight of water, based on the quantity of reaction mixture including water.

This is a continuation, of application Ser. No. 16,684, now abandonedfiled Mar. 1, 1979 which itself is a continuation of application Ser.No. 740,451 filed Nov. 10, 1976, now abandoned.

BACKGROUND OF THE INVENTION

Diisocyanate polyaddition products dispersed in polyethers or polyestersare already known. According to the teaching given in GermanAuslegeschrift No. 1,168,075, diisocyanates are reacted withbifunctional primary alcohols in a dispersing medium consisting of apolyether or polyester having a molecular weight of from 500 to 3000containing at least two, exclusively secondary, hydroxyl groups in themolecule. According to German Auslegeschrift No. 1,260,142, compoundscontaining isocyanate and amino groups are made to undergo apolyaddition reaction in situ in a polypropylene glycol ether asdispersing agent. The dispersions of polyurethanes, polyureas orpolyhydrazodicarbonamides in polyvalent, high molecular weight hydroxylcompounds obtained by the above mentioned processes are recommended asthickeners for the textile or dye industry because of their highviscosities, even at low solid contents. Thus, a 10 or 20% dispersion ofpolyhydrazodicarbonamide in a polypropylene glycol ether obtainedaccording to German Auslegeschrift 1,260,142, for example, has aviscosity of over 10,000 (200,000) cP at 25° C. This amounts to morethan 10 (200) times the viscosity of the pure dispersing agent. Whenattempts are made to prepare a 40% dispersion, the reaction mixturesolidifies before polyaddition has been completed. The high viscositieswhich occur at even relatively low solid contents seriously restrict theuse of the products because, in many fields of application they cannotbe dosed with the usual dosing apparatus. For producing polyurethanefoams, for example, a purpose for which such dispersions have beenrecommended according to an earlier proposal by the present Applicants,the viscosities of the starting materials must be below 2500 cP when theconventional high pressure machines are employed.

According to another earlier proposal, substantially anhydrous,relatively low viscosity dispersions of polyureas and/orpolyhydrazodicarbonamides in polyethers having hydroxyl groups can beobtained if the polyaddition reaction is carried out continuously incontinuous flow mixers. The process has the disadvantage of requiring arelatively complicated technique of dosing and mixing which isuneconomic for customary production rates. Moreover, in some cases highsolids concentrations may give rise to considerable difficulties in theremoval of the heat of reaction.

DESCRIPTION OF THE INVENTION

It has now surprisingly been found that stable dispersions having thedesired low viscosity can be produced in simple stirred apparatus if thepolyaddition reaction is carried out in situ in a mixture of compoundshaving hydroxyl groups and a substantial quantity of water which mayoptionally be removed by distillation after the polyaddition reaction.

A water content of 10, 15 or 20% by weight (based on the total quantityof polyether and water), for example, increases the viscosity of apolyalkylene ether glycol at 25° C. to 4, 8 and 50 times, respectively,the original value (3500, 7300 and over 50,000 cP). If the water contentis further increased, the solution or emulsion originally obtained inmany cases separates into its various phases. Both the high increase inviscosity and the phase separation inevitably led the experts to assumethat the addition of water would be unsuitable for the commercialproduction of low viscosity polyisocyanate polyaddition products incompounds containing hydroxyl groups. This was particularly since it wassuspected that water might also interface chemically with the isocyanatepolyaddition reaction.

The present invention thus relates to a process for the in situpreparation of stable dispersions of polyisocyanate polyadditionproducts in hydroxyl containing compounds as dispersing agents whichcomprises reacting

(1) organic polyisocyanates with

(2) compounds having primary and/or secondary amino groups and/orprimary hydroxyl groups and/or ammonia and, optionally, formaldehyde in,

(3) compounds having at least one hydroxyl group,

compounds (3) containing secondary hydroxyl groups in cases wherecompounds (2) contain primary hydroxyl groups. The components arereacted in the presence of more than 4% by weight, preferably from 7 to35% by weight of water and most preferably from 10 to 25% by weight ofwater, based on the quantity of reaction mixture including water. Ifdesired the water is subsequently removed in known manner.

According to the invention, the compounds used as component (2) arepreferably polyamines and/or hydrazines and/or hydrazides and/orammonia.

In another embodiment of the process according to the invention,reactants (1) and/or (2) may in part consist of monoisocyanates and/orprimary or secondary monoamines and/or monohydrazides for the purpose ofadjusting the product to a given molecular weight. Hydroxyalkylaminesmay also be used in the polyaddition reaction for the same purpose. Inthis way there are also obtained polyurea or polyhydrazodicarbonamideparticles containing reactive groups.

A certain proportion of substances which have an emulsifying action andstabilize the dispersion, such as polyethers containing amino,semicarbazide or hydrazide groups, may also be used.

The present invention relates also to the hitherto unknown stabledispersions, having a solids content of from 10 to 60% by weight, ofpolyureas or polyhydrazodicarbonamides in hydroxyl compounds having amolecular weight of between 62 and 400 or in hydroxyl compoundsessentially consisting of more than 30% by weight and preferably morethan 50% by weight of polyesters and/or polyester amides and/orpolycarbonates having a molecular weight of between 400 and 12,000,preferably between 800 and 8000.

The dispersing agents are the substances forming the external continuousphase in the present invention. They include alcohols having a molecularweight of from about 62 to about 16,000, preferably from 62 to 12,000,and most preferably 106 to 8000 containing from 1 to 8, preferably from2 to 6 and most preferably from 2 to 4 primary and/or secondary hydroxylgroups.

These include, for example, both low molecular weight alcohols orglycols having a molecular weight of between about 62 and about 400 andwhich may also contain ether, thioether of ester bonds and polyesters,polyethers, polythioethers, polyacetals, polycarbonates and polyesteramides having molecular weights of more than 400, such as those knownper se for the production of polyurethanes.

Suitable low molecular weight dispersing agents include monohydricalcohols such as butanol, 2-ethylhexanol, amyl alcohol and ethyleneglycol monoethylether. Diols or triols of the kind conventionally usedas chain lengthening agents or cross-linking agents in polyurethanechemistry are also suitable, e.g. propylene glycol-(1,2) and -(1,3),butylene glycol-(1,4) and -(2,3); hexanediol-(1,6); octane diol-(1,8);neopentyl glycol; cyclohexane dimethanol(1,4-bis-hydroxymethylcyclohexane); 2-methyl-1,3-propanediol; glycerol;trimethylolpropane; hexane triol-(1,2,6); butanetriol-(1,2,4) ortrimethylolethane, and particularly glycols having a hydrophiliccharacter, e.g. ethylene glycol; diethyleneglycol; triethylene glycol ortetraethylene glycol and polyethylene glycols having a molecular weightof up to 400. In addition compounds such as dipropylene glycol,polypropylene glycols having a molecular weight of up to 400, dibutyleneglycol, polybutylene glycols having a molecular weight of up to 400,thiodiglycol and castor oil may also be used as dispersing agentsaccording to the invention. Also suitable are ester diols of the generalformulae

    HO--(CH.sub.2).sub.x --CO--O--(CH.sub.2).sub.y --OH

and

    HO--(CH.sub.2).sub.x --O--CO--R--CO--O--(CH.sub.2).sub.x --OH

in which

R represents an alkylene or arylene group having from 1 to 10 preferably2 to 6 carbon atoms,

x=2 to 6 and

y=3 to 5,

e.g. δ-hydroxybutyl-ε-hydroxy-caproic acid ester;ω-hydroxyhexyl-γ-hydroxybutyric acid ester; adipicacid-bis-(β-hydroxyethyl) ester and terephthalicacid-bis-(β-hydroxyethyl)-ester; as well as diolurethanes of the generalformula

    HO--(CH.sub.2).sub.x --O--CO--NH--R'--NH--CO--O--(CH.sub.2).sub.x --OH

in which

R' represents an alkylene, cycloalkylene or arylene group having from 2to 15, preferably 2 to 6 carbon atoms and

x represents an integer of from 2 to 6, e.g.1,6-hexamethylene-bis-(β-hydroxyethylurethane) or4,4'-diphenylmethane-bis-(δ-hydroxybutylurethane).

Also suitable are diol ureas of the general formula ##STR1## in which

R" represents an alkylene, cycloalkylene or arylene group having from 2to 15 and preferably 2 to 9 carbon atoms,

R'" represents hydrogen or a methyl group and

x=2 or 3,

e.g. 4,4'-diphenylmethane-bis-(β-hydroxyethylurea) or the compound##STR2##

Particularly suitable among the dihydric and trihydric low molecularweight alcohols are those which, either alone or as mixtures or with theaddition of higher molecular weight alcohols, are liquid at temperaturesbelow 50° C.

It has been found that in some cases when low molecular weightdispersing agents and where substantially linear polyisocyanate additioncompounds are used, solutions rather than dispersions are formed. Inthis context, solution means a clear, uniform and homogeneous mixture ofpolyaddition product and dispersing agent. Such solutions are notintended to be covered by the term "dispersion" as used throughout thespecification. It has been found, however, that formation of a solutioncan be easily avoided by the presence of small amounts of water in thedispersing agent. Generally, an amount of water of about 1%, by weight,based on the total weight of the dispersion is sufficient to avoid theformation of a solution. However, as set forth below, the amount ofwater in the dispersions may be varied within wide limits depending onthe particular system involved and the intended use. In most cases,however, the dispersions may be made completely water-free without beingundesirably converted into solutions.

Higher molecular weight hydroxyl polyesters which are suitable asdispersing agents include e.g. reaction products of polyhydric,preferably dihydric alcohols to which trihydric alcohols may be addedand polybasic, preferably dibasic carboxylic acids. Instead of freepolycarboxylic acids, the corresponding polycarboxylic acid anhydridesor polycarboxylic acid esters of lower alcohols or mixtures thereof maybe used for preparing the polyesters. The polycarboxylic acids may bealiphatic, cycloaliphatic, aromatic and/or heterocyclic and they may besubstituted, e.g. by halogen atoms, and/or unsaturated. The followingare mentioned as examples: succinic acid; adipic acid; suberic acid;azelaic acid; sebacic acid, phthalic acid; isophthalic acid; trimelliticacid; phthalic acid anhydride; tetrahydrophthalic acid anhydride;hexahydrophthalic acid anhydride; tetrachlorophthalic acid anhydride;endomethylene tetrahydrophthalic acid anhydride; glutaric acidanhydride; maleic acid; maleic acid anhydride; fumaric acid; dimeric andtrimeric fatty acids such as oleic acid; which may be mixed withmonomeric fatty acids; dimethyl terephthalate andbis-glycolterephthalate. Suitable polyhydric alcohols include e.g.ethylene glycol; propylene glycol-(1,2) and -(1,3); butyleneglycol-(1,4) and -(2,3); hexanediol-(1,6); octane-diol-(1,8);neopentylglycol; cyclohexanedimethanol(1,4-bis-hydroxymethylcyclohexane); 2-methyl-1,3-propanediol; glycerol,trimethylolpropane; hexanetriol-(1,2,6); butanetriol-(1,2,4);trimethylolethane; triethylene glycol; tetraethylene glycol;polyethylene glycols; dipropylene glycol; polypropylene glycols;dibutylene glycol and polybutylene glycols. The polyesters may alsocontain a proportion of carboxyl end groups. Polyesters of lactones,e.g. ε-caprolactam, or hydroxycarboxylic acids, e.g. ω-hydroxycaproicacid, may also be used.

The higher molecular weight polyethers which are preferably used asdispersing agents according to the invention are obtained in knownmanner by reaction of the starting compounds which contain reactivehydrogen atoms with alkylene oxides such as ethylene oxide; propyleneoxide; butylene oxide; styrene oxide; tetrahydrofuran or epichlorohydrinor with any mixtures of these alkylene oxides. In many cases, it ispreferred to use polyethers which contain predominantly primary hydroxylgroups.

Suitable starting compounds containing reactive hydrogen atoms includee.g. water; methanol; ethanol; ethylene glycol; propylene glycol-(1,2)or -(1,3); butylene glycol-(1,4) or -(2,3); hexanediol-(1,6);octanediol-(1,8); neopentyl glycol; 1,4-bis-hydroxymethylcyclohexane;2-methyl-1,3-propanediol; glycerol; trimethylolpropane;hexanetriol-(1,2,6); butanetriol-(1,2,4); trimethylolethane;pentaerythritol mannitol; sorbitol; methyl glycoside; sucrose; phenol;isononylphenol; resorcinol; hydroquinone; 1,2,2- or1,1,3-tris-(hydroxyphenyl)-ethane; ammonia, methylamine; ethylenediamine; tetra- or hexamethylene diamine; diethylenetriamine;ethanolamine; diethanolamine; triethanolamine; aniline;phenylenediamine; 2,4- and 2,6-diaminotoluene andpolyphenylpolymethylene polyamines of the kind obtained byaniline-formaldehyde condensation. Resinous materials such as phenol andresol resins may also be used as the starting materials.

Polyethers modified by vinyl polymers are also suitable for the processaccording to the invention. Products of this kind may be obtained bypolymerizing, e.g. styrene and acrylonitrile in the presence ofpolyethers (U.S. Pat. Nos. 3,383,351; 3,304,273, 3,523,095; 3,110,695and German Pat. No. 1,152,536).

Among the polythioethers which should be particularly mentioned are thecondensation products obtained from thiodiglycol on its own and/or withother glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acidsor aminoalcohols. The products obtained are either polythiomixed ethers,polythioether esters or polythioether ester amides, depending on thecocomponents.

Suitable polyacetals include the compounds which can be prepared fromglycols such as diethylene glycol; triethylene glycol;4,4'-dioxethoxy-diphenyldimethylene; hexanediol and formaldehyde.Polyacetals suitable for the purpose of the invention may also beprepared by the polymerization of cyclic acetals.

Polycarbonates containing hydroxyl groups include those known per sesuch as the products obtained from the reaction of diols such aspropanediol-(1,3), butanediol-(1,4) and/or hexanediol-(1,6),diethyleneglycol, triethylene glycol or tetraethylene glycol withdiarylcarbonates, e.g. diphenylcarbonate, or phosgene.

Suitable polyester amides and polyamides include the predominantlylinear condensates obtained from polyvalent saturated and unsaturatedcarboxylic acids or their anhydrides and polyvalent saturated andunsaturated amino alcohols, diamines, polyamines or mixtures thereof.

As previously mentioned, mixtures of the above mentioned high molecularweight and low molecular weight dispersing agents may of course also beused according to the invention.

The dispersing agents which are preferred according to the invention arethose which are free from any liable groups (e.g. ester groups) whichare liable to be destroyed by hydrolysis or aminolysis in the process ofthe invention. Compounds of this kind are preferably only added to thefinished dispersion after completion of the polyaddition reaction.

The hydroxyl compounds and mixtures thereof used as dispersing agentsaccording to the invention should be chosen so that when mixed with thewater the invention, with any hydroxyl compounds or preferably aminocompounds, and optionally inert solvents, they are liquid at thereaction temperature, i.e. in the form of solutions or emulsions. Theirviscosity at the reaction temperature should generally be below 20,000cP and preferably below 5000 cP so that conventional stirrer and mixingapparatus can be employed.

If inert solvents are to be used, they should preferably distill off asazeotropic mixtures with water, for example, benzene and toluene.

The isocyanate reactive compounds used for the preparation of thedispersions according to the invention are mainly polyamines, hydrazinesand hydrazides. Suitable polyamines include divalent and/or highervalent primary and/or secondary aliphatic, araliphatic, cycloaliphaticand aromatic amines, e.g. ethylene diamine; 1,2- and 1,3-propylenediamine; tetramethylenediamine; hexamethylenediamine; dodecamethylene;diamine; dimethyldiaminohexane; N,N'-dimethylethylenediamine;2,2-bis-aminopropylmethylamine; higher homologues of ethylene diaminesuch as diethylenetriamine; triethylenetetramine andtetraethylenepentamine; homologues of propylenediamine such asdipropylenetriamine; piperazine; N,N'-bis-aminoethylpiperazine;triazine; 4-aminobenzylamine; 4-aminophenylethylamine;1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane;4,4'-diaminodicyclohexyl-methane and -propane; 1,4-diaminocyclohexane;phenylenediamines; naphthylene diamines; condensates of aniline andformaldehyde; tolylene diamines; bis-aminomethylbenzene and derivativesof the above mentioned aromatic amines monoalkylated on one or bothnitrogen atoms. The polyamines generally have a molecular weight of fromabout 60 to about 10,000, preferably 60 to 3000 and most preferably 60to 1000.

Suitable hydrazines include hydrazine itself and monosubstituted orN,N'-disubstituted hydrazines in which the substituents may be C₁ to C₆alkyl groups, cyclohexyl groups or phenyl groups. The hydrazinesgenerally have a molecular weight of from 32 to 500. Hydrazine itself ispreferred.

Suitable hydrazides include the hydrazides of divalent or higher valentcarboxylic acids such as carbonic acid, oxalic acid, malonic acid,succinic acid, adipic acid, sebacic acid, azelaic acid, maleic acid,fumaric acid, phthalic acid, isophthalic acid or terephthalic acid; theesters of hydrazine monocarboxylic acids with divalent or higher valentalcohols and phenols such as ethanediol, propanediol-(1,2),butanediol-(1,2), --(1,3), and --(1,4), hexanediol, diethylene glycol,triethyleneglycol, tetraethylene glycol, dipropylene glycol,tripropyleneglycol and hydroquinone as well as the amides of hydrazinemonocarboxylic acid (semi-carbazides), e.g. with the above mentioneddiamines and polyamines. The hydrazides used generally have a molecularweight of from about 90 to about 10,000, preferably 90 to 3000 and mostpreferably from 90 to 1000.

The amines and hydrazines mentioned above may either be used in the formof their dilute aqueous solutions or as mixtures with the dispersingagent diluted with the necessary quantity of water.

According to a special embodiment of the process of the presentinvention, a stable, finely divided and relatively low viscositydispersion may be produced which is the reaction product of apolyisocyanate, aqueous ammonia and optionally other amino functionalcompounds dispersed in a polyhydroxyl compound as dispersing agent. Theresulting bis-urea may subsequently be converted into a high molecularweight polymethylene urea by cross-linking with formaldehyde.

These polymethylene ureas also form finely divided, stable and lowviscosity dispersions in the hydroxyl compound used as dispersing agent.

The present invention also relates to the resultant novel dispersions ofthe reaction product of polyisocyanates ammonia, optionally otheraminofunctional compounds and optionally formaldehyde in thehydroxyl-containing compound as dispersing agent.

The quantity of polyisocyanate used in this embodiment of the processaccording to the invention is generally 0.5 to 1.5, preferably 0.9 to1.2 and most preferably 1.0 equivalents of polyisocyanate per mol ofammonia. If other amino functional compounds are used in addition toammonia, it is of course necessary to use an additional quantity ofpolyisocyanate approximately equivalent to these amino functionalcompounds.

According to the invention, aqueous ammonia solution is preferred toanhydrous ammonia as starting component, partly because aqueous ammoniais in practice easier to use and partly because any additional aminocompounds used are then more easily distributed in the dispersing agentbecause of the presence of water. Moreover, the polyadduct formed assolid phase has less tendency to agglomeration, so that the finisheddispersion is much more stable.

It is surprising that the bisureas (or trisureas if trifunctionalisocyanates are used) prepared in situ form stable dispersions in thehydroxyl compounds because if, for comparison, urea is introduced in theform of an aqueous solution into a polyhydroxyl compound and the wateris subsequently removed by distillation, urea crystallizes in the formof coarse needles. Such a suspension of urea crystals cannot be used asa starting component for the production of polyurethane resins.

In a preferred variation of the process of the invention, the bisurea ortrisurea dispersion prepared in situ is cross-linked to a polymethyleneurea by means of formaldehyde in the presence of a catalytic quantity ofan acid or alkali in known manner, as described, for example, in GermanOffenlegungsschrift No. 2,324,134. The quantity of formaldehyde used forthis purpose is generally 0.2 to 3 mol, preferably 0.4 to 1.5 mol, mostpreferably 0.5 to 0.8 mol per equivalent of urea groups.

According to the invention, the formaldehyde may also be added at thesame time as the ammonia solution. The products then obtained aredifferent in their physical properties from those obtained by the abovedescribed process where there is subsequent cross-linking withformaldehyde. They are disperse systems with a microgel character. Inthis variation of the process of the invention, it is necessary toensure either that all of the components are mixed together at the sametime or that the polyisocyanate is introduced into the reaction mixtureimmediately after the formaldehyde and ammonia solution has been mixedin the dispersing agent, i.e. before ammonia and formaldehyde havereacted to form urotropin.

The starting components used according to the invention also includealiphatic, cycloaliphatic, araliphatic, aromatic and heterocyclicpolyisocyanates such as those described, for example, by W. Siefken inJustus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example,ethylene diisocyanate; 1,4-tetramethylene diisocyanate;1,6-hexamethylene diisocyanate; 1,12-dodecane diisocyanate;cyclobutane-1,3-diisocyanate; cyclohexane-1,3- and -1,4-diisocyanate andany mixtures of these isomers;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane as describedin German Auslegeschrift No. 1,202,785 and U.S. Patent 3,401,190; 2,4-and 2,6-hexahydrotolylene diisocyanate and any mixtures of theseisomers; hexahydro-1,3- and/or -1,4-phenylene diisocyanate;perhydro-2,4'- and/or -4,4'-diphenylmethane diisocyanate; 1,3- and1,4-phenylenediisocyanate; 2,4- and 2,6-tolylene diisocyanate and anymixtures of these isomers; diphenylmethane-2,4'- and/or4,4'-diisocyanate; naphthylene-1,5-diisocyanate;triphenylmethane-4,4',4"-triisocyanate; polyphenyl-polymethylenepolyisocyanates of the kind which can be obtained by anilineformaldehyde condensation followed by phosgenation and which have beendescribed, for example, in British Patent Nos. 874,430 and 848,671, m-and p-isocyanatophenylsulphonylisocyanates according to U.S. Pat. No.3,454,606; perchlorinated aryl polyisocyanates such as those describede.g. in German Auslegeschrift No. 1,157,601 and U.S. Pat. No. 3,277,138;polyisocyanates containing carbodiimide groups as described in GermanPat. No. 1,092,007 and U.S. Pat. No. 3,152,162; diisocyanates of thekind described in U.S. Pat. No. 3,492,330, polyisocyanates havingallophanate groups as described, e.g. in British Pat. No. 994,890;Belgian Pat. No. 761,626 and published Dutch Patent Application No.7,102,524; polyisocyanates having isocyanurate groups as described e.g.in U.S. Pat. No. 3,001,973; German Pat. Nos. 1,022,789; 1,222,067 and1,027,394 and in German Offenlegungsschriften Nos. 1,929,034 and2,004,048; polyisocyanates with urethane groups, e.g. as described inBelgian Pat. No. 752,261 and U.S. Pat. No. 3,394,164; polyisocyanateshaving acylated urea groups according to German Patent 1,230,778;polyisocyanates with biuret groups as described e.g. in German Pat. No.1,101,394; U.S. Pat. Nos. 3,124,605 and 3,201,372 and British Pat. No.889,050 polyisocyanates prepared by telomerization reactions asdescribed e.g. in U.S. Pat. No. 3,654,106; polyisocyanates with estergroups, for example, those mentioned in British Pat. Nos. 965,474 and1,072,956; U.S. Pat. No. 3,567,763 and German Patent 1,231,688; reactionproducts of the above mentioned isocyanates with acetals according toGerman Pat. No. 1,072,385 and polyisocyanates containing polymeric fattyacid groups according to U.S. Pat. No. 3,455,883.

The distillation residues containing isocyanate groups obtained from thecommercial production of isocyanates may also be used, if desired assolutions in one or more of the above mentioned polyisocyanates. Anymixtures of the above mentioned polyisocyanates may also be used.

It is generally preferred to use commercially readily availablepolyisocyanates, for example, 2,4- and 2,6-tolylene diisocyanate and anymixtures of these isomers ("TDI"); polyphenyl-polymethylenepolyisocyanates which can be prepared by aniline-formaldehydecondensation followed by phosgenation ("crude MDI"); and polyisocyanateswhich have carbodiimide groups, urethane groups, allophanate groups,isocyanurate groups, urea groups or biuret groups ("modifiedpolyisocyanates").

So-called prepolymers may, of course, also be used as isocyanatecomponents according to the invention, i.e. reaction products of lowmolecular weight and/or higher molecular weight compounds havinghydroxyl and/or amino groups, e.g. those of the kind mentioned above,with an excess of the monomeric polyisocyanates described above.

Some or all of the isocyanates or amines, hydrazines or hydrazides usedin the process according to the invention may also have a functionalityhigher than 2. It must be regarded as surprising that the reactionaccording to the invention of such higher functional compounds indispersing agents which have hydroxyl groups does not result in solid orat least very highly viscous reaction products but rather gives rise tofinely divided, low viscosity dispersions.

The polyaddition products produced by the process of the invention whichare dispersions in compounds containing hydroxyl groups may, as alreadymentioned above, be modified by the addition of a proportion ofmonofunctional isocyanates, amines, hydrazine derivatives or ammonia.

Thus, for example, the average molecular weight of polyaddition productscan be adjusted as desired by the incorporation of such monofunctionalcompounds. Polyureas or polyurea polyhydrazodicarbonamides containingfree hydroxyl groups can be obtained by using alkanolamines havingprimary or secondary amino groups. The introduction of other groups suchas ester groups, longer aliphatic groups, tertiary amino groups, activedouble bonds, etc. can also be achieved by the addition of suitablysubstituted monoamines, diamines or isocyanates.

Suitable monofunctional isocyanates include e.g. alkyl isocyanates suchas methyl; ethyl; isopropyl; isobutyl; hexyl; lauryl and stearylisocyanate; chlorohexyl isocyanate; cyclohexyl isocyanate; phenylisocyanate; tolyl isocyanate; 4-chlorophenylisocyanate anddiisopropylphenylisocyanate.

Suitable monoamines include e.g. alkylamines and dialkylaminescontaining C₁ -C₁₈ alkyl groups; cycloaliphatic amines such ascyclohexylamine and its homologues; aniline and N-alkylanilines andaniline derivatives which are substituted in the benzene ring;alkanolamines such as ethanolamine, diethanolamine, propanolamine,dipropanolamine, butanolamine and dibutanolamine and diamines having atertiary and a primary or secondary amino group, e.g.N,N-dimethylethylene-diamine and N-methylpiperazine. Suitablemonofunctional hydrazine derivatives and hydrazides include e.g.N,N-dialkylhydrazines, the hydrazides of monocarboxylic acids, hydrazinemonocarboxylic acid esters of monofunctional alcohols or phenols, andsemicarbazides, e.g. methyl, ethyl, propyl, butyl, hexyl, dodecyl,stearyl, phenyl and cyclohexylsemicarbazide.

The molecular weight of the polyaddition products prepared according tothe invention as dispersions in hydroxyl compounds is determined by theproportion by weight of polyamine, hydrazine or hydrazide on the onehand to polyisocyanate on the other (and monofunctional compounds ifadded). It is particularly preferred to react approximately equivalentquantities of isocyanates and hydroxyl functional or preferably aminofunctional compounds in the hydroxyl containing dispersing agents. Chainlengthening agents which have primary hydroxyl groups are reacted in adispersing agent containing exclusively secondary hydroxyl groups. Alimited excess of isocyanate may also be used but the products thenobtained have a relatively high viscosity, increasing with the amount ofisocyanate excess used, since the excess of polyisocyanate reacts withthe dispersing agent. Low molecular weight chain lengthening agents suchas amine, hydrazine or hydrazide, on the other hand, may be used inlarge excess without causing an increase in the viscosity. Polyadditionproducts having reactive end groups and a limited molecular weight areobtained in such cases. The equivalent ratio of polyisocyanate to chainlengthening agent is generally kept between about 0.50 and about 1.50,preferably between 0.90 and 1.10. It is particularly preferred to useapproximately equivalent quantities.

When polyisocyanates are reacted with polyamines, hydrazines orhydrazides in the presence of compounds having hydroxyl groups, theisocyanate groups react very preferentially with the amino groups but acertain proportion of the hydroxyl groups of the dispersing agent alsotake part in the reaction, depending on the reaction conditions. Thisreaction gives rise to polyurea and/or polyhydrazodicarbonamide chainswhich are chemically linked with the monohydric or, preferably,polyhydric alcohol used as dispersing agent. Such end groups presumablyhave a dispersing action on the solid particles. The extent to which thehydroxyl groups take part in the polyaddition reaction dependsparticularly on the reaction temperatures and on the water content. Iftoo large a number of higher molecular weight polyol molecules reactwith the polyisocyanates, highly viscous dispersions are obtained. Thisoccurs in the process described in German Auslegeschrift 1,260,142. Onthe other hand, if the proportion of polyol molecules taking part in thereaction is too low, the larger particles of the resulting dispersionsare liable to be unstable and undergo sedimentation. The processaccording to the invention has the surprising effect of making itpossible to adjust the proportion of the NCO/OH reaction so that finelydivided dispersions having the required low viscosity are obtained butat the same time coarser particles in the dispersion are stillsufficiently stable so that they will not undergo sedimentation evenduring prolonged storage at elevated temperatures.

If, however, the reaction is carried out using low viscosity polyetherscontaining exclusively secondary hydroxyl groups or less reactive(aliphatic) isocyanates, the proportion of polyol molecules taking partin the polyaddition reaction may be too low to result in a stabledispersion. In such cases it is advisable to include emulsifyingsubstances in the polyaddition reaction so that the stability of thedispersion will be increased. These emulsifying substances includelinear polyethers having an average molecular weight of 300 to 4000 andcarrying isocyanate groups or amino or hydrazide groups at both ends ofthe chain or preferably only at one end.

For example, minor quantities of isocyanate adducts of diols having thefollowing general formula ##STR3## may be used as emulsifying agents. Inthe above formula, R represents a divalent group such as can be obtainedby removal of the isocyanate group from a diisocyanate having amolecular weight of from about 112 to about 1000;

X represents oxygen or --NR"--,

R' and R", which may be the same or different, represent monovalenthydrocarbon groups having from 1 to 12 carbon atoms,

R'" represents hydrogen or a monovalent hydrocarbon group having from 1to 8 carbon atoms,

R^(IV) represents a hydrogen atom or a methyl group and

n represents an integer of from 4 to 89.

The preparation of such emulsifying diols has been described, forexample, in German Offenlegungsschrift No. 2,314,512.

Modified polyethers used as dispersing agents according to the inventioninclude those having the above general formula and also, for example,addition products of excess diisocyanates and/or polyisocyanates of thekind mentioned above with monofunctional and/or bifunctional hydroxylpolyethers having an average molecular weight of from 300 to 4000, whichmay be freed from unreacted free isocyanate by thin layer evaporation.If desired, these isocyanate prepolymers may also be reacted with excessfree isocyanate to form allophanate isocyanates. Addition productscontaining isocyanate end groups may also be converted into polyetherscontaining amino or semicarbazide end groups by reaction with excessdiamines or hydrazine, e.g. according to German Auslegeschrift No.1,122,254 and 1,138,200.

Polyethers containing amino end groups, e.g. those prepared by theprocess according to U.S. Patent 3,155,278 or German Auslegeschrift No.1,215,373, may also be used as dispersing agents according to theinvention.

Lastly, hydroxyl polyethers may be reacted with phosgene to convert theminto chloroformic acid esters which may then be reacted with excessdiamine or hydrazine. As already mentioned above, polyethers which carryan isocyanate or amino group at only one chain end are preferred asdispersing agents.

The modified polyethers which have a dispersing action are generallyonly added in quantities of up to about 15% by weight, preferably onlyup to 3% by weight (based on the total quantity of polyol and solidcontent) to the particularly preferred dispersions according to theinvention which have a solids content of about 10 to 60% by weight. Ifthe dispersions have a higher or lower solids content, a correspondinglylarger or smaller quantity of dispersing agent is used.

According to a less preferred variation of the process of the invention,compounds of the type mentioned above having two or more primaryhydroxyl groups and a molecular weight of from 62 to 400 may be reactedwith isocyanates (optionally together with monohydric primary alcohols)to produce polyurethane dispersions. In that case, however, it should benoted that only dispersing agents which contain exclusively secondaryhydroxyl groups may be used and they should preferably have a molecularweight of more than about 500 in order to ensure selective reaction ofthe polyisocyanate with the primary hydroxyl compounds.

The quantity of water which should be present during the polyadditionreaction is of decisive importance in determining the particle size, theparticle size distribution and the final viscosity of the dispersion.Several factors must be taken into account simultaneously: the viscosityand hydrophilic or hydrophobic character of the dispersing agentcontaining alcoholic groups, the solubility or emulsifiability of thestarting components used for the isocyanate polyaddition reaction, thesolids content of the resulting dispersion and the temperaturesemployed. The sequence and method of addition may also be of someinfluence. With increasing water content, a significant increase inviscosity occurs, particularly if a somewhat hydrophilic highermolecular weight dispersing agent is used. This effect becomes morepronounced with progressive polyaddition in alcohol diluted with water.The maximum quantity of water which may be added is therefore limited.In all cases it is necessary to ensure that the reaction mixture isvigorously mixed in the presence of water during the polyadditionreaction and during the subsequent removal of water by distillation. Thequantity of water added would generally be less than 35% by weight butat least about 7% by weight, based on the total quantity of reactionmixture (the higher the desired solid content of the dispersion, themore water should be added). The optimum quantity of water is that whichresults in the lowest possible final viscosity of the dispersion butwhich does not require the removal of unnecessarily large quantities ofwater by distillation. The preferred quantity of water is in many casesbetween 10 and 25% by weight, based on the reaction mixture. Smallerquantities of water, upwards of about 4% by weight, may be used if thealcohols are strongly hydrophilic.

For obtaining a very low final viscosity, it is also advantageous toemploy a very high reaction temperature from the start of thepolyaddition reaction, preferably a temperature close to the boilingpoint of water.

When using stirrer vessels with reflux condensers, the heat produced inthe strongly exothermic isocyanate reaction can easily be removed byboiling under reflux. At the same time, any adducts formed in thegaseous phase above the liquid reaction mixture can be continuouslywashed into the liquid phase by the water while still in statu nascendiand finely dispersed therein.

Various methods may be employed for mixing the dispersing agent with thereactants. In the simplest case, the hydroxyl containing dispersingagent, the necessary quantity of water and the amino compound, orprimary hydroxyl compound, are introduced into a stirrer vessel andheated with stirring, for example to 70°-90° C. The isocyanate componentis then added rapidly so that the reaction mixture boils vigorouslyunder reflux. When producing dispersions with a high solids content, itis advantageous to introduce the polyisocyanate or polyisocyanatemixture into the lower third of the liquid in the reaction vessel. Ifsuitable stirrer apparatus are employed, the reaction temperature may beraised to 105° to 115° C. by employing a slight excess pressure. Whenthe isocyanate groups have undergone complete reaction, the water andany inert solvent present are distilled off at reduced pressure and thedispersion is discharged through a sieve. In many cases, the aminecompound optionally dissolved in water and the polyisocyanate may, ofcourse, be introduced simultaneously into the mixture of dispersingagent and water. In that case, however, any excess of isocyanate shouldbe avoided. Part of the heat of reaction may be used up, for example, bymixing the polyisocyanates with part of the alcohol used as dispersingagent at room temperature immediately before it is added to the reactionmixture. If the process according to the invention is desired to becarried out continuously, for example, in the case of a large scalecommercial production of more than 1000 tons/mo., the dispersing agent,the various reactants and water may be continuously fed into continuousflow mixers. In view of the strongly exothermic nature of the reaction,which increases with increasing solid content, and hence the increasingvapor pressure, the residence time in the reactor must be so short thatthe reaction temperature in the premixer as far as possible does notexceed 100° C. When preparing a 40% dispersion, for example, the timerequired for the flow through the mixer should not be substantiallyabove 1 to 3 seconds. The premixed reactants are then introduced into afinal stirrer vessel in which they stay for 20 to 30 minutes beforebeing forced into another vessel for removal of the water bydistillation.

Distillation of the water may also be carried out at a later stage, butthe resulting dispersions then have a higher viscosity.

For obtaining very low viscosities, it is preferred practice to use thediscontinuous process followed by immediate removal of water bydistillation. This affords great simplicity, reliability in reactioncontrol and reproducibility.

The quantity of water required for subsequent reactions, such aspreparation of polyurethane foams, may of course be left in the finisheddispersion.

The concentration of polyaddition products in the dispersing agentcontaining hydroxyl groups may vary within a wide range but is generallybetween about 1 and about 60% by weight and particularly between 5 and50% by weight. The dispersions prepared according to the invention haveviscosities of up to 80,000 cP and preferably up to 40,000 cP at 25° C.,depending on their concentration. After dilution to a solids content of10% by weight, they generally have a viscosity below 2500 and preferablybelow 1500 cP at 25° C. It is a special advantage of the processaccording to the invention that in many cases dispersions prepared atvery high concentrations have a relatively lower viscosity afterdilution with the same dispersing agent than comparable productsprepared from the start with low solids contents.

According to the invention, dispersions with a surprisingly high solidscontent (up to 50% or more) can be prepared economically in stirrervessels with reflux condensers in spite of the strongly exothermicreaction of isocyanate groups with amino groups. Since dispersions witha solids content of about 10% by weight are generally used for producingpolyurethane resins, it is possible to mix the concentrated dispersionswith large proportions by weight of those hydroxyl containing alcohols,e.g. polyesters, which might partially react with water or aminocompounds, e.g. by hydrolysis or aminolysis at the temperatures at whichpreparation of the dispersion is carried out. Thus, for example, a 20%(10% ) dispersion in which the proportion by weight of polyether topolyester is 3:5 (1:5) and which has a viscosity only slightly higherthan that of the pure polyester or even lower can be obtained from a 40%polyhydrazodicarbonamide dispersion in polyether by stirring an equalquantity or three times the quantity of polyester into it (see Example7).

It is surprisingly found that these dispersions in polyol mixtures arestable even if under otherwise identical conditions, the polyethers andpolyesters are not miscible with each other. The polyurethane solidscontent dispersed in the product evidently acts as emulsifier,preventing separation of the system into two phases even duringprolonged storage. This is another important advantage of the processaccording to the invention since it makes it possible for novelpolyurethane resin products not obtainable by any other method to beproduced from such stabilized polyester/polyether systems.

The use of higher molecular weight hydroxyl polyethers as dispersingagents in the process according to the invention makes possible, asalready mentioned above, a highly economic and variable method ofcommercial production. The process is carried out under mild conditionsto produce dispersions having a high solids concentration which may, ifdesired, be used as master batches. The use of polyethers has, however,yet another important advantage: The large scale commercial productionof polyethers leads in most cases to the formation of intermediatestages of aqueous crude polyethers which have a water content of from 8to 12% and which contain 0.3 to 1% by weight of alkali metal sulphatesin solution and 1 to 3% by weight of toluene in suspension. Such a crudepolyether suspension is normally distilled under reduced pressure toreduce the water and toluene to a residue of from 0.4 to 1% by weight.The alkali metal sulphates are thereby precipitated and can be removedby means of sponge filters.

The polyether now free from sulphates and containing 0.5 to 1% by weightof water is substantially freed from its residual water by thin layerevaporation so that the water content of the purified commercialpolyether is less than 0.5% by weight. For the process according to theinvention, however, it is not necessary to use a highly purified,practically anhydrous polyether. The preliminary stages of crudepolyether are satisfactory for the process. Either the substanceobtained before thin layer evaporation or, what is particularlyadvantageous, the so-called crude polyether suspension (containing about10% of water alkali metal sulphate and toluene) are suitable. In theprocess according to the invention, the water, toluene and sulphate areremoved by distillation and filtration after termination of theisocyanate polyaddition reaction.

According to another possible variation of the present invention,polyisocyanate polyaddition products dispersed in the polyhyroxylcompounds are subsequently cross-linked with formaldehyde in knownmanner in the presence of catalytic quantities of acids. It issurprisingly found that cross-linked dispersions of this kind are alsofinely disperse and stable in storage.

The special importance of the present invention lies in the fact thatall the above mentioned improvements and modifications in the propertiesof polyurethane resins can be obtained using the usual raw materials andconventional, in most cases standardized, formulations.

The dispersions prepared by the process according to the invention canbe used as "modified" lower or higher molecular weight polyhydroxylcompounds in known manner in reactions with polyisocyanates of the kindmentioned above, if desired together with unmodified polyhydroxylcompounds or polyamines, hydrazines or hydrazides of the kind mentionedabove as chain lengthening agents, blowing agents, catalysts and otheradditives to produce polyurethane resins with improved mechanicalproperties. Examples of the products which may be produced includefoams, elastomers, homogeneous and porous coatings, lacquers andthermoplastic polyurethanes. In addition, the products of the processmay be used as they are or after conversion to "modified" prepolymers byreaction with a polyisocyanate excess for producing aqueous polyurethanedispersions by known methods.

One factor which is of major importance in determining the improvementin properties of the resulting polyurethane resins, particularly theimprovement in compression resistance, is the particle size of thedispersed polyaddition products. For example, when using polyetherdispersions as starting material for the production of polyurethanefoams, the diameter of the particles of filler must be substantiallybelow the dimensions of the cell walls (20 to 50 μm). In polyurethanecoatings, the particles must also be small enough to ensure that evenvery thin coatings will have a smooth surface and be applied evenly.

The process according to the invention advantageously gives rise todispersions having particle sizes of from 0.01 to 5 μm, preferably 0.1to 1 μm, which satisfy the commercial requirements.

The following examples serve to explain the process according to theinvention. The figures given represent parts by weight or percentages byweight unless otherwise indicated.

EXAMPLE 1

20% Polyhydrazodicarbonamide dispersion in trifunctional polyether:##EQU1## Reaction mixture:

80.0 parts by weight of a polyether of propylene oxide and ethyleneoxide started on trimethylolpropane and having a hydroxyl number of 34and containing about 80% of primary hydroxyl groups (hereinafterreferred to as "polyether I") as dispersing agent;

16.9 parts by weight of tolylene diisocyanate (isomeric mixture of 2,4-:2,6=80:20; hereinafter referred to as "T 80");

3.1 parts by weight of hydrazine (as 99% hydrate, optionally dilutedwith water before it is added to the reaction mixture).

Water content: see Table 1.

General Method

The dispersing agent preheated to 70° C. and the hydrazine hydratediluted with water are mixed in a stirrer vessel equipped with refluxcondenser and heated to 80° C. with stirring. The diisocyanate mixtureis then rapidly introduced into the stirrer cone. Polyaddition sets inat once with vigorous boiling of the water under reflux. After additionof the diisocyanate, the temperature is lowered to 60°-80° C. within 20to 30 minutes, if necessary with cooling, and the water is distilled offat reduced pressure. The temperature is allowed to rise to 90° to 120°C. towards the end of the reaction until no more water distills over.The reaction mixture is then filtered through a 100 μm sieve when theviscosity allows it (Examples 1b and 1c).

                                      TABLE 1                                     __________________________________________________________________________    % by weight of water based on  Viscosity                                           Reaction mixture                                                                       Dispersing                                                                          Solids                                                                            Dispersion                                                                           25° C. (cP)                             Example                                                                            (including water)                                                                      agent content                                                                           (anhydrous)                                                                          20%   Appearance                               __________________________________________________________________________    1a   4.8      6.3   25.2                                                                              5.0    268.000                                                                             Paste                                    1b   7.9      10.7  42.7                                                                              8.5    2.700 Finely divided                                                                dispersion                               1c   11.3     16.0  64.0                                                                              12.8   2.315 Finely divided                                                          1.350 (+)                                                                           dispersion                               __________________________________________________________________________     (+) Diluted to a solids content of 10% by the addition of polyether I    

Comparison Example 1d

When Example 1 is repeated without the addition of water but underotherwise identical conditions, the reaction mixture becomes pasty evenduring the addition of diisocyanate.

Comparison Example 1e

When Example 1 is repeated with 50% by weight of water in the reactionmixture, phase separation takes place. The reaction mixture becomespasty on removal of water.

EXAMPLE 2

40% polyhydrazodicarbonamide dispersion in trifunctional polyether.

The formulation of the reaction mixture is similar to that in Example 1but adjusted to a solids content of 40%.

At a water content of 20% by weight, based on the reaction mixtureincluding water (this amounts to 41.5% by weight or 62% by weight or 25%by weight, based on dispersing agent or on solids content or onanhydrous dispersion), a very finely divided dispersion (0.3 to 2 μm) isobtained, which has a viscosity of 12,800 cP/25° C. when the residualwater content is 0.4% (when diluted with additional polyether I to asolids content of 20% or 10%, the viscosity is 1550 or 1050 cp/25° C.).

Reaction conditions

The method of Example 1 is modified in that the process is carried outin a 500 l stirrer vessel and the diisocyanate mixture is introduced atslight pressure not into the stirrer cone but into the lower third ofthe vessel.

Comparison experiment

Without the addition of water, the reaction mixture becomes pasty andthe stirrer is brought to a standstill even before the total quantity ofdiisocyanate has been added.

EXAMPLE 3

20% Modified polyhydrazodicarbonamide dispersion in trifunctionalpolyether; Index=100

Formulation of reaction mixture:

80.0 Parts by weight of polyether I;

1.43 parts by weight of diisocyanate T 80;

3.2 parts by weight of diol urea ether of the formula ##STR4## 3.5 partsby weight of hydrazine (in the form of 99% hydrazine hydrate; addedafter dilution with water) and a total of

11.9% by weight of water, based on the reaction mixture (=16.8% based ondispersing agent; 67.4% based on solids content; 13.5% based onanhydrous end product).

The method is similar to that of Example 1 but the diol urea ether ispreviously reacted with an excess of diisocyanate (index 200) at 100° C.and the remaining quantity of diisocyanate T 80 is added to it aftercooling and the resulting mixture is introduced into the receiver.

The resulting very finely divided polyol dispersion has a viscosity of2120 cP/25° C. at a residual water content of 0.5% by weight.

EXAMPLE 3a

Index=100

Formulation of reaction mixture:

80.0 Parts by weight of a polyether (polyether II) of propylene oxideand ethylene oxide (hydroxyl number=35; about 70% of primary hydroxylgroups) which has been started on trimethylolpropane:

14.3 parts by weight of diisocyanate T 80;

4.4 parts by weight of diethylene glycol;

1.3 parts by weight of hydrazine (as 99% hydrate; introduced into thereceiver as a dilution with water); and a total of

13.7% by weight of water, based on the reaction mixture including water(=19.8% based on dispersing agent; 73.4% based on solids content; 15.9%based on anhydrous end product).

The method is similar to that of Example 1 but a prepolymer is firstprepared from diethylene glycol and part of the diisocyanate (index 200)and the remaining diisocyanate is then added to the prepolymer before itis introduced into the reaction mixture.

The viscosity of the resulting finely divided, substantially anhydrous20% dispersion is 2670 cP/25° C.

EXAMPLE 4

A 38.3% dispersion in a linear polyether of an OH functionalpolyhydrazodicarbonamide polyurea. ##EQU2##

Formulation of reaction mixture:

61.7 parts by weight of a linear polypropylene glycol having secondaryhydroxyl groups (hereinafter referred to as polyether III; OHnumber=56);

31.0 parts by weight of diisocyanate T 80;

5.2 parts by weight of hydrazine (as 99% hydrazine hydrate; added as adilution with water);

2.1 parts by weight of ethanolamine; a total of

22.3% by weight of water, based on the reaction mixture including water(=46.5% based on dispersing agent: 75.1% based on solids content; 27.8%based on anhydrous dispersion).

The method is similar to that of Example 2.

The resulting stable polyether dispersion which has a residual watercontent of 0.2% by weight and a concentration of 40% has a viscosity of2460 cP at 25° C. or when diluted to 20% with the polyether used it hasa viscosity of 680 cP/25° C. or when diluted to 10% with the polyetherused the viscosity is 510 cP/25° C.

EXAMPLE 4a

The formulation given in Example 4 is modified in a similar manner toExample 3, but using as prepolymer the reaction product of thediisocyanate with 3% by weight of the dispersing agent (based on thetotal solids content). The dispersion obtained is even more finelydivided than that of Example 4 and it has excellent flow properties.

EXAMPLE 5

A 40%, highly cross-linked polyurea-polyhydrazodicarbonamide dispersionin trifunctional polyether;

Index=100.

Formulation of reaction mixture:

60.0 parts by weight of polyether I;

31.0 parts by weight of diisocyanate T 80;

2.9 parts by weight of hydrazine (added as hydrazine hydrate dilutedwith water);

6.1 parts by weight of diethylene triamine; a total of

18.9% by weight of water, based on the reaction mixture including water(=38.9% based on dispersing agent; 58.4% based on solids content; 23.3%based on anhydrous end product).

The stable dispersion prepared in a similar manner to Example 1 has aviscosity of 18,500 (3,800 or 2,200) cP/25° C. at 40% (20% or 10%).

EXAMPLE 6

20% Polyhydrazodicarbonamide dispersion in polyester;

Index=100.

Formulation of reaction mixture:

80 parts by weight of a polyester of adipic acid, trimethylol propaneand diethylene glycol (hydroxyl number=56; acid number=1; hereinafterreferred to as polyester ATD);

16.9 parts by weight of diisocyanate T 80;

3.1 parts by weight of hydrazine (added as hydrazine hydrate dilutedwith water); a total of

11.3% by weight of water, based on the reaction mixture including water(=16% based on dispersing agent; 64% based on solids content; 12.8%based on anhydrous polyester dispersion).

The method is similar to that of Example 1. A stable dispersion isobtained. Its viscosity at a solids content of 20% is 35,000 cP/25° C.and at 10% the viscosity is 24,500 cP/25° C. The pure polyester has aviscosity of 21,400 cP/25° C.

Comparison experiment

If no water is introduced into the receiver before the diisocyanate isadded so that only the small quantity of water from the undilutedhydrazine hydrate is present, the reaction mixture completely solidifieseven before all the diisocyanate has been added.

EXAMPLE 7

Dispersion in a polyether/polyester mixture.

If the solids content of the 38.3% dispersion from Example 4 is reducedto 20% by weight or 10% by weight, respectively, by stirring polyesterATD (viscosity 21,400 cP/25° C.) into the dispersion, a stablepolyether/polyester mixture having a viscosity of 19,800 or 24,200cP/25° C. is obtained.

A mixture of pure polyether III and polyester ATD (without any soliddispersed in it), on the other hand, separates into two phases afteronly a few hours.

EXAMPLE 8

20% polyurethane dispersion in polyether containing secondary OH groups;Index=100

Formulation of reaction mixture:

80.0 parts by weight of polyether III;

11.8 parts by weight of diisocyanate T 80;

8.2 parts by weight of N-methyl diethanolamine;

7% by weight of water, based on the reaction mixture including water(=9.4% based on dispersing agent: 37.5% based on solids content; 7.5%based on anhydrous dispersion).

Method

Polyether, N-methyldiethanolamine and water are introduced into thestirrer apparatus at room temperature and the diisocyanate is addedslowly with cooling so that the reaction temperature does not rise above50° C. One hour after all the isocyanate has been added, the water isdistilled off at reduced pressure. The temperature may gradually beraised to 90° C. towards the end of distillation.

The viscosity of the resulting stable 20% dispersion is 2.210 cP/25° C.

Comparison experiment

When the process is carried out without the addition of water to thereaction mixture but under otherwise identical reaction conditions, thedispersion obtained sediments overnight.

EXAMPLE 9

20% polyhydrazodicarbonamide dispersion in trifunctional polyether

Formulation of reaction mixture:

80.0 parts by weight of a polyether of propylene oxide and ethyleneoxide (Hydroxyl number 28; approximately 80% of primary (hydroxylgroups) which has been started on trimethylolpropane;

7.1 parts by weight of tolylene diisocyanate; (isomeric mixture2,4:2,6=65:35);

10.2 parts by weight of 4,4'-diphenylmethane diisocyanate;

2.7 parts by weight of hydrazine (as 99% hydrate; introduced afterdilution with water); a total of

13.0% by weight of water, based on the reaction mixture including water(=18.6% based on dispersing agent; 74.5% based on solids content; 14.9%based on anhydrous end product).

Method

The polyether is used in the form of a crude polyether suspensioncontaining 10.5% of water and 0.5% of alkali metal sulphate and mixedwith the hydrazine hydrate. Polyaddition takes place in situ as a resultof the addition of a mixture of the above mentioned diisocyanates underthe conditions specified in Example 1.

The resulting 20% dispersion which is stable and substantially anhydroushas a viscosity of 4200 cP/25° C. After dilution to 10% with a furtherquantity of (anhydrous) polyether, it has a viscosity of 2100 cP/25° C.

EXAMPLE 10

The method is completely similar to that of Example 9 but purediphenylmethane diisocyanate is replaced by a crude MDI. The viscosityof the 20% and 10% stable dispersions, respectively, is 3200 and 1900cP/25° C.

EXAMPLE 11

100 parts by weight of the polyhydrazodicarbonamidepolyether dispersionaccording to Example 1c adjusted to a solids content of 20%.

3.0 parts by weight of water,

0.2 parts by weight of triethylene diamine,

0.3 parts by weight of 2-dimethylamino-ethanol, 0.8 parts by weight ofcommercial polysiloxane foam stabilizer (OS 15 of Bayer AG) and

0.22 parts by weight of tin-(II)-octoate

were mixed together. This mixture was vigorously stirred at roomtemperature with

24.1 parts by weight of tolylene diisocyanate (65% 2,4- and 35%2,6-isomer) and

12.0 parts by weight of tolylene diisocyanate (80% 2,4- and 20%2,6-isomer).

A creamy reaction mixture formed after 8 to 9 seconds. Its rise time was75 seconds and its gel time 120 seconds.

The resulting foam was found to have the following mechanicalproperties:

    ______________________________________                                        Gross density according to DIN 53 420                                                                     33 kg/m.sup.3                                     Tensile strength according to DIN 53 571                                                                  160 KPa                                           Elongation at break according to DIN 53 571                                                               190%                                              Compression reistance according to DIN 53 577                                                             5.3 KPa                                           Indentation hardness according to ASTM D 1564-71T:                            H-value at 25% deformation (N)                                                                            290                                               H-value at 65% deformation (N)                                                                            540                                               RH-value at 25% deformation (N)                                                                           200                                               (25% RH-value/25% H-value) × 100                                                                    70%                                               65% H-value/25% H-value     1.9                                               ______________________________________                                    

Comparison experiment

The same formulation was used except that the polyhydrazodicarbonamidedispersion was replaced by 100 parts by weight of polyether I used asdispersing agent. Observing the same ratio of NCO/OH groups (index), afoam of the same gross density is obtained but its compressionresistance according to DIN 53 577 is only 4.8 KPa.

EXAMPLE 12

100 parts by weight of the dispersion from Example 1c,

5.0 parts by weight of water,

0.2 parts by weight of triethylene diamine,

0.3 parts by weight of 2-dimethylamino-ethanol,

1.0 parts by weight of polysiloxane foam stabilizer (OS 15 of BAYER AG)and

0.2 parts by weight of tin-(II)-octoate

were mixed together. The resulting mixture was then stirred togetherwith

28.55 parts by weight of tolylene diisocyanate (65% 2,4- and 35%2,6-isomer) and

28.55 parts by weight of tolylene diisocyanate (80% 2,4- and 20%2,6-isomer)

at room temperature.

A creamy reaction mixture having a rise time of 55 seconds and a geltime of 100 seconds was obtained after 6-7 seconds.

The resulting foam was found to have the following mechanicalproperties:

    ______________________________________                                        Gross density according to DIN 53 420                                                                     24 kg/m.sup.3                                     Tensile strength according to DIN 53 571                                                                  140 KPa                                           Elongation at break according to DIN 53 571                                                               180%                                              Compression resistance according to DIN 53 577                                                            4.1 KPa                                           Indentation hardness according to ASTM D 1564-71T:                            H-value at 25% deformation  130                                               H-value at 65% deformation  255                                               RH-value at 25% deformation 95                                                (25% RH-value/25% H-value) × 100                                                                    73%                                               65% H-value/25% H-value     2.0                                               ______________________________________                                    

EXAMPLE 13

100 parts by weight of the dispersion from Example 1c adjusted to asolids content of 10%,

3.0 parts by weight of water,

0.1 part by weight of triethylene diamine,

0.3 part by weight of 2-dimethylamino-ethanol,

1.0 part by weight of polysiloxane foam stabilizer (OS 15 of Bayer AG)and

0.18 parts by weight of tin-(II) octoate

were mixed together. The resulting mixture was vigorously stirredtogether with

19.2 parts by weight of tolylene diisocyanate (65% 2,4- and 35%2,6-isomer) and

19.2 parts by weight of tolylene diisocyanate (80% 2,4- and 20%2,6-isomer)

at room temperature. A creamy reaction mixture having a rise time of 102seconds and a gel time of 180 seconds was obtained after 10 seconds.

The resulting foam was found to have the following mechanicalproperties:

    ______________________________________                                        Gross density according to DIN 53 420                                                                     34 kg/m.sup.3                                     Tensile strength according to DIN 53 571                                                                  150 KPa                                           Elongation at break according to DIN 53 571                                                               200%                                              Compression resistance according to DIN 53 577                                                            5.1 KPa                                           Indentation hardness according to ASTM D 1564-71T:                            H-value at 25% deformation  275                                               H-value at 65% deformation  510                                               RH-value at 25% deformation 180                                               (25% RH-value/25% H-value) × 100                                                                    65                                                65% H-value/25% H-value     1.9                                               ______________________________________                                    

EXAMPLE 14

100 parts by weight of the dispersion from Example 1c 5.0 parts byweight of water,

0.1 part by weight of triethylene diamine,

0.3 part by weight of 2-dimethylamino-ethanol,

1.2 parts by weight of polysiloxane foam stabilizer (OS 15 of Bayer AG)and

0.2 parts by weight of tin-(II) octoate

were mixed together.

The resulting mixture was vigorously stirred together with

28.85 parts by weight of tolylene diisocyanate (65% 2,4- and 35%2,6-isomers) and

28.85 parts by weight of tolylene diisocyanate (80% 2,4- and 20%2,6-isomer)

at room temperature.

A creamy reaction mixture having a rise time of 60 seconds and a geltime of 100 seconds was obtained after 8 seconds.

The resulting foam was found to have the following mechanicalproperties:

    ______________________________________                                        Gross density according to DIN 53 420                                                                     23 kg/m.sup.3                                     Tensile strength according to DIN 53 571                                                                  140 KPa                                           Elongation at break according to DIN 53 571                                                               190%                                              Compression resistance according to DIN 53 577                                                            3.9 KPa                                           Indentation hardness according to ASTM D 1564-71T:                            H-value at 25% deformation  110                                               H-value at 65% deformation  235                                               RH-value at 25% deformation 80                                                (25% RH-value/25% H-value) × 100                                                                    72                                                65% H-value/25% H-value     1.9                                               ______________________________________                                    

EXAMPLE 15

100 parts by weight of the stable polyurea-polyhydrazodicarbonamidedispersion (polyester:polyether=5:1) from Example 7 adjusted to a solidscontent of 10%,

4.0 parts by weight of water,

0.6 parts by weight of dimethylbenzylamine,

0.1 parts by weight of Sn-(II)-octoate and

2.0 parts by weight of a commercial polysiloxane foam stabilizer (OS 25of Bayer AG)

were mixed together.

The resulting mixture was intimately stirred together with

52.5 parts by weight of diisocyanate T 80 at room temperature.

A creamy reaction mixture having a rise time of 65 seconds and a geltime of 125 seconds was obtained after 10 seconds.

The resulting foam has open cells in contrast to pure polyester foams,which generally have closed cells, and on account of its uniform, veryfine cell structure it is suitable, for example, as filter material.

When the example is repeated with a mixture of pure polyester andpolyether mixed in the same proportions without polyurethane solidsdispersed therein, an open celled foam is again obtained but its cellsare substantially larger with the cell membranes still partly present.

The mixture of pure polyester and polyether is moreover not stable instorage, as already mentioned earlier. When left to stand at roomtemperature, it separates into two phases within a short time.

EXAMPLE 16

Homogeneous polyurethane sheets

(a) Preparation of a prepolymer

89.7 parts by weight of the 40% polyether dispersion from Example 2 arereacted with

10.3 parts by weight of diisocyanate T 80 at 100°-110° C. until the freeisocyanate content is 3.0% by weight.

The resulting prepolymer has a viscosity of 24,800 cP/25° C. and isstable in storage at room temperature.

(b) Preparation of a polyurethane elastomer

The prepolymer is mixed with 0.2% by weight of tin-(II) octoate andspread out on a glass plate to form a layer 500 μm in thickness, using adoctor knife. The product obtained after heat treatment at 110°-130° C.(30-60 minutes) is a film which has good mechanical properties and isresistant to organic solvents.

(c) Solvent-free coating

When the same prepolymer is mixed with less than the equivalent quantityof ethanolamine by 5 equivalent % in a small capacity continuous flowhigh speed stirrer and the mixture is applied to a separating paper toform a layer 500 μm in thickness by the reversal process, using a doctorknife, the elastomer formed in this process solidifies within a fewseconds in an infra-red channel. While the layer is still tacky, atextile substrate is placed on it under light pressure and thepolyaddition reaction is completed in a heating channel with thetemperature falling from 180° C. to 120° C.

The coated fabric obtained in this way is highly resistant to abrasionand organic solvents.

Comparison experiments

When a prepolymer containing 3% of free isocyanate groups is preparedfrom the pure dispersing agent (polyether I) by a similar method toExample 16 and heated with the catalyst under otherwise identicalconditions and cooled to room temperature, one merely obtains atransparent, sticky elastomer mass which has no structural stability andcannot be stripped from its substrate.

The addition of ethanolamine results in a similar sticky product.

EXAMPLE 17

10% dispersion of aromatic BHS (bisurea) in tri-functional polyether.

Formulation

936 parts by weight of polyether I;

68 parts by weight of a 25% aqueous ammonia solution;

87 parts by weight of T 80.

Water content

4.7% by weight, based on the reaction mixture including water.

Method and reaction conditions

The dispersing agent and aqueous ammonia solution are introduced at roomtemperature (18° to 25° C.) into a vessel equipped with stirrer andreflux condenser. Diisocyanate T 80 is added directly to the liquidphase of the mixture, with stirring, so that the temperature rises to50°-70° C. as a result of the exothermic polyaddition reaction.Distillation of water at reduced pressure can be begun as soon as theaddition of isocyanate has been completed. The hot, anhydrous dispersionis discharged through a 100 μ sieve.

The dispersion has a viscosity of 2560 cP at 25° C.

EXAMPLE 17a

Example 17 is repeated under the same conditions and using the samestarting components but with a water content of 10% by weight in thereaction mixture and using the quantity of polyether I required toproduce a 20% dispersion. The resulting anhydrous 20% dispersion has aviscosity of 7430 cP at 25° C. immediately after it has been prepared.If left to stand for some time at room temperature, its viscositygenerally rises to a considerable extent but can be reduced to itsoriginal value by 5 minutes' stirring at room temperature. Afterdilution to a solid content of 10% with additional polyether I, thedispersion has a viscosity of 2050 cP at 25° C. The viscosity of this10% dispersion remains constant even during prolonged storage.

EXAMPLE 18

10% aromatic bis-urea dispersion in trifunctional polyether.

Formulation

1917 parts by weight of polyether I;

102 parts by weight of 25% aqueous ammonia solution;

187.5 parts by weight of 4,4'-diisocyanatodiphenylmethane (hereinafterreferred to as "D 44");

Water content

3.5 percent by weight.

Reaction conditions

Diisocyanate D 44 heated to a temperature of from 90° to 110° C. isintroduced into the mixture of dispersing agent and ammonia solution asdescribed in Example 17 and the water is then distilled off.

The viscosity of the 10% dispersion is 25° C. at 3610 cP.

EXAMPLE 19

20% aromatic bis-urea dispersion in a linear polyether.

Formulation

416 parts by weight of a linear propylene glycol (hydroxyl number 56) asdispersing agent;

68 parts by weight of 25% aqueous ammonia solution;

87 parts by weight of diisocyanate T 80%;

Water content

8.9 percent by weight.

The method is the same as in Example 17. The 20% dispersion has aviscosity of 1930 cP at 25° C. This viscosity does not change evenduring prolonged storage.

EXAMPLE 20

20% aromatic bis-urea dispersion in a linear polyether.

Formulation

1136 parts by weight of the polyether described in Example 19,

136 parts by weight of 25% aqueous ammonia solution;

56 parts by weight of water;

250 parts by weight of diisocyanate D 44.

Water content

10% by weight.

The reaction conditions are the same as indicated in Example 18. Thefinely divided 20% dispersion has a viscosity of 1960 cP at 25° C.

EXAMPLE 20a

20.9% PMU (polymethyleneurea) dispersion in linear polyether.

If the bis-urea dispersion from Example 20 is left to react for one hourat 70° to 95° C. with the quantity of aqueous formalin solution requiredto provide one formaldehyde molecule for every two urea groups in thepresence of a catalytic quantity of 85% phosphoric acid, optionallybefore the water is distilled off, a polymethylene urea dispersion isobtained which, when anhydrous and at a solids content of 20.9% (10%),has a viscosity of 2860 cP (1680 cP) at 25° C.

EXAMPLE 21

20% aliphatic bis-urea dispersion in a linear polyether.

Formulation

808 parts by weight of the polyether described in Example 19;

136 parts by weight of 25% aqueous ammonia solution;

10 parts by weight of water;

168 parts by weight of hexamethylene-1,6-diisocyanate.

Water content

10 percent by weight.

Preparation of the dispersion is carried out by the method described inExample 17.

At 25° C. the anhydrous 20% (15%, 10%) dispersion has a viscosity of9800 cP (1750 cP, 1040 cP).

EXAMPLE 22

20% aromatic bis-urea dispersion in monoethylene glycol.

Formulation

416 parts by weight of monoethylene glycol,

68 parts by weight of 25% aqueous ammonia solution,

87 parts by weight of diisocyanate T 80.

Water Content

8.9 percent by weight.

Preparation of the dispersion is carried out as described in Example 17.As can be seen from the following table, the viscosity of the aqueousdispersion varies considerably both with solids content and withtemperature.

    ______________________________________                                        Solids content                                                                              Temperature  Viscosity                                          (% by weight) (°C.) (cP)                                               ______________________________________                                        20            25           highly viscous                                                                paste                                              20            50           270                                                17.5          50           150                                                17.5          40           175                                                ______________________________________                                    

EXAMPLE 23

20% aromatic bis-urea dispersion in monoethylene glycol

Example 20 is repeated but using 1136 parts by weight of monoethyleneglycol instead of the polyether described in Example 19.

Viscosity of the finely divided stable dispersion at 25° C. (dependingon the solids content):

    ______________________________________                                        Solids content (% by weight)                                                                    20     17.5      15   10                                    Viscosity (cp)   1200    700      200   71                                    ______________________________________                                    

EXAMPLE 24

Continuous method of carrying out the process of Example 1.

The reactants are continuously fed into a reaction vessel from twostorage vessels B 1 and B 2. Vessel B 1 contains a mixture of 10,000parts by weight of polyether I, 612 parts by weight of hydrazine hydrateand 1380 parts by weight of water and vessel B 2 contains 2113 parts byweight of diisocyanate T 80.

The rate of feed is 119.90 g per minute from B 1 and 21.13 g per minutefrom B 2. The combined rate of feed is therefore 141.03 per minute.

Method

Using a twin piston pump, the mixture which is heated to 95° C. in B 1and the diisocyanate from B 2, which is kept at 20° C., are combinedcoaxially in a static mixer (manufactured by Kenics; diameter 1/4 inch;21 elements; volume approximately 3 ml) (residence time in mixer about1.3 seconds) and the mixture is delivered at a preliminary pressure of 2to 3 bar into a steel reaction tube about 6 m in length. The diameter ofthis tube is about 9 mm and the temperature inside the tube is kept to130°±5° C. by heating or cooling.

The reaction tube ends in a separating vessel in which the practicallyanhydrous dispersion is restirred at a pressure of 20 Torr and atemperature of 70° C. during an average residence time of about 4 to 8minutes. The separating vessel is connected to a distillation bridgeand, via a pump, to another vessel used as receiver for the end product.

The resulting, finely divided, 20% dispersion has a viscosity of 2460 cPat 25° C.

Example 24a (Comparison experiment)

When Example 24 is repeated without using water, the reaction mixturealready solidifies inside the static mixer so that delivery into themultiphase flow tube is practically impossible.

EXAMPLE 25

20% polyhydrazodicarbonamide dispersion in castor oil.

Formulation

80.0 parts by weight of castor oil;

16.9 parts by weight of diisocyanate T 80;

3.1 parts by weight of hydrazine (in the form of an aqueous solution ofhydrazine hydrate); a total of

11.3 parts by weight of water.

The method is the same as that described in Example 1. The viscosity ofthe 20% dispersion at 25° C. is 5950 cP.

EXAMPLE 25a (Comparison experiment)

When Example 25 is repeated with a total water content in theformulation of only 1.8% by weight, based on the total mixture, thereaction product becomes pasty during removal of the water bydistillation, and finally becomes rubbery.

EXAMPLE 26

Modification of a dispersion according to Example 1c with formaldehyde

A 37% aqueous formaldehyde solution (10% by weight of formaldehyde,based on the solids content of the dispersion) and a catalytic quantityof 85% phosphoric acid are added to the 20% polyhydrazodicarbonamidedispersion from Example 1c, optionally before the water is distilledoff, and the mixture is gradually heated to 80°-90° C. The water isfinally distilled off at reduced pressure.

The dispersion, which is substantially free from formaldehyde, ispractically unchanged in its low viscosity at 25° C. and can be used forproducing polyurethane foams which have improved compression resistance.

EXAMPLE 27

The procedure is the same as described in Example 26 but 10% by weightof an aqueous solution of dimethylolurea, based on the solids content,is used instead of an aqueous formaldehyde solution for subsequentmodification of the polyhydrazodicarbonamide dispersion.

The modification increases the viscosity of thepolyhydrazodicarbonamides dispersion by only about 5%.

EXAMPLE 28

20% hydrazodicarbonamide-bis-urea dispersion in polyether III.

Formulation

80.0 parts by weight of polyether III;

1.1 parts by weight of hydrazine (used as hydrazine hydrate diluted withwater);

1.2 parts by weight of ammonia (added as 25% aqueous solution); a totalof

11.2 parts by weight of water;

17.7 parts by weight of 4,4'-diisocyanatodiphenylmethane.

Method

The dispersing agent and the aminofunctional compounds dissolved inwater are introduced at room temperature into a stirrer apparatusequipped with reflux condenser, and the diisocyanate, which has beenheated to about 100° C., is directly introduced into the liquid phase ofthe mixture with vigorous stirring. The reaction temperature rises toabout 65°-75° C. Water is then removed at reduced pressure. Theresulting finely divided, 20% dispersion has a viscosity at 1920 cP at25° C.

The dispersion can easily be modified by aftertreatment withformaldehyde in a similar manner to Example 26 to yield a dispersionwith only slightly increased viscosity and containing polymethylene ureagroups.

What is claimed is:
 1. A process for the in situ preparation of a stabledispersion of non-ionic polyisocyanate-polyaddition products in hydroxylcontaining compounds as dispersing agent by a process which comprisesreacting the following components;(1) at least one organicpolyisocyanate with (2) at least one compound selected from the groupconsisting of compounds having a group selected from the groupconsisting of primary amino groups, second amino groups, primaryhydroxyl groups, and ammonia in (3) an alcohol selected from the groupconsisting of an alcohol containing 2 to 8 primary hydroxyl groups, analcohol containing 2 to 8 secondary hydroxyl groups, and mixturesthereof, wherein compounds (3) have secondary hydroxyl groups whencompounds (2) have primary hydroxyl groups and wherein the componentsare reacted in the presence of more than 4% by weight of water, based onthe quantity of reaction mixture including water.
 2. The process ofclaim 1, wherein compound (2) additionally includes formaldehyde.
 3. Theprocess of claim 1, further comprising the step of removing the water.4. The process of claim 1, wherein the compound used as component (2) isselected from the group consisting of at least difunctional amines,hydrazines, hydrazides, ammonia and mixtures thereof.
 5. The process ofclaim 1, wherein the substances used as components (1) and (2) include aproportion of compounds selected from the group consisting ofmonoisocyanates, primary or secondary monoamines, monohydrazides, andmixtures thereof.
 6. The process of claim 1, wherein inert organicsolvents are used to reduce the viscosity of the reaction mixture. 7.The process of claim 1, wherein said dispersing agent is an unpurifiedcrude polyether containing water, organic solvents and alkali metalsalts, obtained from the commercial production of polyether-polyols. 8.The process of claim 1, wherein the reaction of components (1) and (2)in dispersing agent (3) is carried out batchwise in stirrer vessels withreflux condensers.
 9. The process of claim 1, wherein compound (2) isammonia.
 10. The process of claim 9, wherein, in addition to ammonia,other amino functional compounds are used as component (2).
 11. Theprocess of claim 9, wherein formaldehyde is added to the reactionmixture at any point in the process.
 12. The process of claim 10,wherein formaldehyde is added to the reaction mixture at any point inthe process.
 13. The process of claim 1, wherein said dispersing agent,component (3), has a molecular weight of at least
 62. 14. The stabledispersion product of the process of claim 1.